Lab 1: A Dehydrogenation/Hydrogenation Reaction Discussion: The aromatic product is a phenol derivative formed from reacting the R-carvone with

Pd/C. According to the 1H NMR of the product of the reaction, there are 6 equivalent hydrogen atoms as opposed to 3 in carvone; this suggests that the double bond of the bottom isopropenyl group must have been broken. Next, the 13C[1H] NMR of the product shows that the highest ppm of carbon is 153.19 instead of 198.49, which means that the carbonyl was turned into an alcohol. Since these two double bonds were broken, more hydrogen bonds were formed. However, the 1H NMR of carvone and that of the product indicate that both compounds contain 14 hydrogen atoms. Therefore, to preserve the amount of hydrogen bonds, the cyclohexene gives up two equivalents of hydrogen to yield benzene; the product is a phenol with methyl and isopropyl substituents. Since the molecular weight of the product is 150 g/mol and 0.0009 moles of R-carvone were reacted, the theoretical yield is (150 g/mol) (0.0009 mol), which is equal to 0.135 grams. (0.135 g)

The actual yield was 0.055 grams; thus, the percent yield of the product is (0.055 g) (100%) = 40.7%. Starting with the enol form of carvone, an approximate

equals the energy of new

bonds formed plus the energy of bonds broken. In this reaction, benzene was formed and a terminal alkene was hydrogenated. Dehydrogenating 1,3-cyclohexadiene to benzene requires -26 kcal mol-1, and hydrogenating the terminal alkene requires -126 kcal mol-1, which adds up to a total of -152 kcal mol-1. The reaction is exothermic. To isolate and purify the product from this reaction, the cooled reaction mixture of carvone and Pd/C was first diluted with hexane to ease filtration of the Pd/C. Then NaOH was

added, resulting in an acid-base reaction that deprotonated the hydroxyl group and negatively ionized the product, allowing it to separate from the organic hexane solvent and dissolve into the aqueous layer. At this point, the pH was between 11 and 12 (basic). Next, HCl was added to neutralize the base; in other words, it re-protonated and regenerated the product in the aqueous layer; the pH became 1 (acidic). Diethyl ether was added to separate the product, which is more soluble in ether, from the aqueous HCl. The product in the top ether layer was isolated and dried over Na2SO4 to remove excess water. Finally, the diethyl ether which evaporates easily was removed with a gentle stream of air, leaving the isolated product.

Conclusion: The purpose of this lab was to determine if transfer-hydrogenation reactions are limited to hydrocarbon starting materials or if they are applicable to cyclohexanone to obtain a phenol. After carrying out and observing the reaction of R-carvone with Pd/C and heat, the product a phenol derivative was identified using methods including NMR spectroscopy and TLC. The experiment demonstrates that a phenol can be produced from a cyclohexanone through dehydrogenation and hydrogenation, resulting in a resonance-stabilized benzene derivative. Also, it was valuable to be able to practice isolation of a product through ionizing and neutralizing the hydroxyl group.

Questions: 1. No, the outcome of the reaction would not be different if S-carvone was used instead of Rcarvone because the original compound loses its stereochemistry. The dehydrogenation of the

ring yields a benzene derivative, and the ring itself becomes planar with all planar substituents. Thus, R-S stereochemistry is not reflected in the product. 2. Disregarding TLC, a couple of other observations suggest that a reaction occurred during the experiment. First, bubbling was observed when the initial compound was heated with Pd/C, and the heated reaction mixture darkened and developed a tar-like consistency. Physically, the R-carvone was a minty, colorless liquid, while the product smelled like oregano and was a rich golden-yellow liquid. 3. There will be a stronger interaction between the hydroxyl and isopropyl groups in compound B. When comparing the 1H NMR spectra of the molecules, the corresponding peak will have a smaller chemical shift (it will be up-field compared to that peak for compound A). 4. For the compound isolated from the hexane phase, the molecular ion at m/z = 154 suggests that it is a saturated compound without double bonds. The product isolated from the hexane layer has a carbonyl group, since it had a peak at 198 ppm in the 13C NMR spectrum. Thus, the product in the hexane layer lacks the carbon-carbon double bond, leaving an isopropyl group. Please see the back of this page for the balanced equation of the reaction. 5. The reaction of the ketone with Pd/C at elevated temperatures leads to no reaction because the di-substituted methyl groups strengthen the effects of keto-enol tautomerism. This occurs because the carbonyl group is present alternate to a double bond; the ketone group is intermittently converted into an alcohol group and thus no reaction takes place.